JP2003206452A - Adhesive composition for semiconductor device, adhesive sheet for semiconductor device using the same, substrates for connecting semiconductors and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new adhesive composition for semiconductor devices that has excellent thermal cycle reliability, reflow resistance and workability, an adhesive sheet for semiconductor devices using the same, semiconductor devices in an industrial scale and increase the reliability of the semiconductor devices and improve the productivity. <P>SOLUTION: In the sheet-form adhesive composition, the ratio (A/B) of haze (A) after the thermal setting at 170°C for 2 hours to the B-stage haze (B) is kept at ≥1.2. An adhesive sheet for semiconductor devices is provided by using the composition. Further, the substrate for connecting semiconductors and semiconductor devices are provided by using the adhesive sheets. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a semiconductor connecting substrate such as a tape automated bonding (TAB) type pattern processing tape and a ball grid array (BGA) package interposer used for mounting a semiconductor integrated circuit. , Lead frame fixing tape, L
Adhesion of electronic components such as OC fixing tapes and semiconductor elements to supporting members such as lead frames and insulating supporting substrates, that is, die bonding materials, heat spreaders, reinforcing plates, adhesives for shield materials, solder resists, anisotropic conductive films, The present invention relates to an adhesive composition suitable for producing a copper-clad laminate, a coverlay, etc., an adhesive sheet using the same, a semiconductor connecting substrate, and a semiconductor device.

[0002]

2. Description of the Related Art A method using a metal lead frame is most widely used for mounting a semiconductor integrated circuit (IC). In recent years, IC connection is made on an organic insulating film such as glass epoxy or polyimide. There is an increasing number of methods in which a semiconductor connection substrate called an interposer, in which a conductive pattern for a substrate is formed, is used.

The package forms include a dual in-line package (DIP), a small outline package (SOP), and a quad flat package (QF).
Package forms such as P) have been used. But I
With the increase in the number of pins of C and the miniaturization of packages, the QFP, which can maximize the number of pins, is approaching its limit.
Therefore, BGA in which connection terminals are arranged on the back surface of the package
(Ball grid array) and CSP (chip scale package) have come to be used.

As a method of connecting the semiconductor connecting substrate, there are a tape automated bonding (TAB) method, a wire bonding method, a flip chip method and the like.

Therefore, TA is used for the semiconductor connection substrate.
A tape with an adhesive for B can be used. The BGA method is particularly suitable for a process of mechanically punching holes for solder balls and device holes for ICs and then laminating a copper foil after mechanically punching holes for solder balls and device holes for ICs. On the other hand, in the case of wire bonding and flip chip connection without inner leads, not only the tape with adhesive for TAB,
It is also possible to use a copper-clad laminate in which copper foil is already laminated and the adhesive is heat-cured.

FIG. 1 shows an example of the BGA system. The BGA method is characterized in that it has solder balls, which correspond to the number of pins of the IC, on a grid (grid array) as an external connection portion of a semiconductor integrated circuit connecting substrate to which the IC is connected. The connection to the printed circuit board is performed by placing the solder ball surface on the conductor pattern of the printed circuit board on which the solder has already been printed so as to match and melting the solder by reflow. The greatest feature is that the surface of the interposer can be used, so that many terminals can be arranged in a small space as compared with a package that can use only the peripheral side such as QFP. To further advance this miniaturization function,
Chip scale package (CSP), micro BGA (μ-BGA), fine pitch BGA (FP-)
BGA), memory BGA (m-BGA), board-on-chip (BOC), and other structures have been proposed. μ-BG
A is characterized by emitting a beam lead from the interposer and connecting to the IC. In m-BGA, BOC (FIG. 1) and FP-BGA, the IC and the interposer are connected by wire bonding. The wire bonding connection is difficult to deal with a fine pitch, but it does not require complicated beam lead processing and a wire bonder for a conventional lead frame can be used, which is advantageous in terms of cost. An adhesive, that is, a die bonding material is also used when bonding the IC and the interposer of the package having these structures.

Further, a component such as a reinforcing plate (stiffener) for imparting rigidity and flatness or a heat radiating plate (heat spreader) for radiating heat may be laminated on the semiconductor connection substrate. Also glue is used.

With the progress of miniaturization and high density of electronic devices, these adhesives often remain in the package in the end, so that various adhesive properties, heat resistance, thermal cycle property, etc. It is required to meet the characteristics.

Further, the above-mentioned semiconductors are often produced in large quantities at one time, and when a thermosetting type adhesive is used as the above-mentioned adhesive, a thermosetting step is required. In the production equipment of this step, means for confirming whether the adhesive has been cured as specified is required as intended, and if there is an index that can be easily determined whether it has been cured, it is industrially effective. For μ-BGA, etc., TAB
After laminating the adhesive sheet on the tape, it may be inspected whether the adhesive is embedded in the pattern or whether air bubbles or foreign substances are mixed in, but in such a case, before curing the adhesive In this state, the wiring pattern of the semiconductor connection substrate and the like must be visually recognizable, and further, the visibility in the inspection of air bubbles and foreign matter defects mixed during bonding is also necessary. Therefore, it is extremely important that the adhesive layer and the protective film before curing have good transparency.
In addition, if the operator can judge whether the adhesive is cured or not by just seeing the difference in transparency, it can be used as a process control index.

[0010]

However, in the conventional adhesive composition, a composition which can contribute to the industrial productivity improvement in the above-mentioned form has not been obtained. There is no significant change in transparency both before and after curing, and even if it is transparent enough to allow a visual inspection for pattern embedding, there is no change in transparency during the curing process. It did not become the standard to judge.

The present invention solves the above problems and further provides a novel adhesive composition for semiconductor devices, which is excellent in thermal cycle property and reflow resistance, and an adhesive sheet for semiconductor devices using the same, for semiconductor connection. It is an object to provide a substrate and a semiconductor device.

[0012]

Means for Solving the Problems That is, the present invention provides a sheet-shaped adhesive composition in which a haze change ratio between a haze (A) after heat curing at 170 ° C. for 2 hours and a B-stage haze (B) ( A / B) is 1.2 or more, which is an adhesive composition for a semiconductor device, and an adhesive sheet for a semiconductor device, a semiconductor connecting substrate and a semiconductor device using the same.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The constitution of the present invention will be described in detail below.
In order to achieve the above-mentioned object, the present invention diligently studied the optical characteristics (transparency), long-term heat resistance characteristics, elastic modulus characteristics, and softening behavior of an adhesive component of a semiconductor device adhesive composition before and after heat curing. As a result, by controlling the mixed state of the thermoplastic resin and the thermosetting resin and skillfully combining the curing agent of the thermosetting resin, it has excellent thermal cycleability and reflow resistance, and the change in transparency before and after curing can be visually observed. It is an adhesive composition for semiconductor devices that can be recognized in the above.

The adhesive composition for a semiconductor device and the adhesive sheet for a semiconductor device according to the present invention are used when mounting the above-mentioned stiffener, heat spreader, semiconductor element or semiconductor integrated circuit for a wiring board (interposer). , Tape Automated Bonding (TA
B) type patterned tape, semiconductor connecting substrate such as ball grid array (BGA) package interposer, lead frame fixing tape, LOC fixing tape, electronic parts such as semiconductor element and lead frame and insulating support substrate, etc. Adhesive composition suitable for bonding with supporting member, that is, die bonding material, heat spreader, reinforcing plate, adhesive for shield material, solder resist, anisotropic conductive film, copper-clad laminate, coverlay, etc. This is an adhesive sheet using the same, and the shape and material of the adherend are not particularly limited. Among them, the adhesive composition in the present invention is a wiring board layer (a semiconductor integrated circuit (bare chip) divided into an insulating layer and a conductor pattern after an element is formed on a semiconductor substrate (C) such as silicon ( This is effective for a semiconductor device having a structure in which the semiconductor integrated circuit (D) and the wiring board layer (A) are bonded to A) with the adhesive layer (B) of the present invention and connected by wire bonding. (A) is an electrode pad of the bare chip and the outside of the package (printed circuit board,
TAB tape, etc.), which is a layer having a conductor pattern for connecting the conductor pattern, and in which the conductor pattern is formed on one side or both sides of the insulator layer. The insulator layer here is polyimide, polyester, polyphenylene sulfide, polyether sulfone, polyether ether ketone, aramid, polycarbonate, polyarylate,
A flexible insulating film having a thickness of 10 to 125 μm and a ceramic substrate made of alumina, zirconia, soda glass, quartz glass, or the like, which is made of a composite material such as plastics or epoxy resin-impregnated glass cloth, and the like, are preferable. A plurality of layers selected from may be laminated and used. If necessary, the insulating layer may be subjected to surface treatment such as hydrolysis, corona discharge, low temperature plasma, physical roughening, and easy adhesion coating treatment.

The formation of the conductor pattern is generally performed by either the subtractive method or the additive method, but either method may be used in the present invention. In the subtractive method, a metal plate such as a copper foil is adhered to the insulating layer with an insulating adhesive (the adhesive composition of the present invention can also be used), or the metal plate is covered with the insulating layer. A pattern is formed by stacking precursors and etching a material prepared by a method of forming an insulating layer by heat treatment or the like by a chemical treatment. Specific examples of the material here include a copper-clad material for rigid or flexible printed boards and a TAB tape. on the other hand,
In the additive method, a conductor pattern is directly formed on the insulator layer by electroless plating, electrolytic plating, sputtering or the like. In any case, the formed conductor may be plated with a metal having high corrosion resistance to prevent corrosion. Via holes may be formed in the wiring board layer (A) thus formed, if necessary, and the conductor patterns formed on both surfaces by plating may be connected by plating.

The adhesive layer (B) is an adhesive layer mainly used for bonding the wiring board layer (A) and the semiconductor substrate (C). However, it is not limited to be used for bonding the wiring board layer (A) to other members (for example, IC and heat sink). This adhesive layer is usually laminated on the semiconductor integrated circuit connecting substrate in a semi-cured state. Before or after lamination, the adhesive layer is preliminarily cured at a temperature of 30 to 200 ° C. for an appropriate time to improve the degree of curing. It can be adjusted. This adhesive layer is formed from the adhesive composition for a semiconductor device of the present invention (hereinafter referred to as an adhesive composition), and has a haze (A) after being heat-cured at 170 ° C. for 2 hours and a B-stage haze (B). It is preferable that the haze change ratio (A / B) of (1) is 1.2 or more, and more preferably 1.8 or more. When the change ratio is lower than 1.2, it is difficult to understand the change in transparency,
It is difficult to confirm the change visually. The haze is calculated by dividing the haze (A) after heating and curing at 170 ° C. for 2 hours in the sheet-shaped adhesive composition and dividing the reference haze by the B-stage haze (B) (A / B). The haze value of the B-stage haze (B) of the sheet-shaped adhesive composition is preferably 80 or less, more preferably 50 or less. If higher than 80,
It is difficult to visually confirm wiring pattern embedding, bubbles, foreign matter, etc. Since the haze may be influenced by the thickness, the film thickness for haze measurement is 50 in the present invention.
μm is good. Of course, if it is thinner than 50 μm, then 5
Even if it is thicker than 0 μm, if the haze value and the haze change ratio described above are satisfied, it is possible to obtain the effect due to the change in transparency such as visual confirmation of change, and thus it is included in the scope of the present invention. . The haze in the present invention is used as an index of transparency (cloudiness value). The haze here excludes the influence of scattering due to surface irregularities, and when the adhesive surface is not smooth, it is attached to a glass plate for measurement. Regarding the measuring method, JISK71
According to 05.

Further, the adhesive composition of the present invention preferably has an adhesive force after heat curing of 5 Ncm ^-1 or more, more preferably 10 Ncm ^-1 or more. If the adhesive strength after heat curing is lower than 5 Ncm ^-1 , peeling may occur during handling of the package or the reflow resistance may decrease, which is not preferable.

The thickness of the adhesive layer can be appropriately selected depending on the relationship between the elastic modulus and the linear expansion coefficient, but it is preferably 2 to 500 μm, more preferably 20 to 200 μm.

The adhesive composition of the present invention preferably contains at least one type of thermoplastic resin and at least one type of thermosetting resin, but the types are not particularly limited. Thermoplastic resin has functions such as adhesiveness, flexibility, relaxation of thermal stress, and improvement of insulation due to low water absorption. Thermosetting resin has heat resistance, insulation at high temperature, chemical resistance, adhesion. It is necessary to realize the balance of physical properties such as the strength of the agent layer.

As the thermoplastic resin, acrylonitrile-butadiene copolymer (NBR), acrylonitrile-
Butadiene rubber-styrene resin (ABS), polybutadiene, styrene-butadiene-ethylene resin (SEB
S), acrylic acid having a side chain of 1 to 8 carbon atoms and /
Alternatively, methacrylic acid ester resin (acrylic rubber), polyvinyl butyral, polyamide, polyester, polyimide, polyamideimide, polyurethane, etc. are exemplified. Further, these thermoplastic resins may have a functional group capable of reacting with a thermosetting resin described later. Specifically, it is an amino group, a carboxyl group, an epoxy group, a hydroxyl group, a methylol group, an isocyanate group, a vinyl group, a silanol group or the like. These functional groups are preferable because they strengthen the bond with the thermosetting resin and improve the heat resistance. Further, acrylic acid and / or methacrylic acid ester having a side chain having 1 to 8 carbon atoms is used as an essential copolymerization component from the viewpoints of adhesiveness with the material of the wiring board layer (A), flexibility, and thermal stress relaxation effect. The copolymer can be used particularly preferably. Further, these copolymers may also have a functional group capable of reacting with a thermosetting resin described later. Specifically, it is an amino group, a carboxyl group, an epoxy group, a hydroxyl group, a methylol group, an isocyanate group, a vinyl group, a silanol group or the like. Furthermore, in this case, a copolymer having a carboxyl group and / or a hydroxyl group as a functional group,
It is more preferable to use a mixture of copolymers having other functional groups. Regarding the functional group content, 0.07 eq / k
It is preferably g or more and 0.7 eq / kg or less, more preferably 0.07 eq / kg or more and 0.45 eq / kg or less, still more preferably 0.07 eq / kg or more and 0.14 eq.
/ Kg or less.

The amount of the thermoplastic resin added to the adhesive composition of the present invention is preferably 2 to 80% by weight, more preferably 5%.
˜70% by weight, more preferably 10 to 60% by weight. If it is less than 2% by weight, flexibility cannot be obtained, and if it exceeds 80% by weight, heat resistance is insufficient, and thus neither is preferable.

Examples of the thermosetting resin include known resins such as epoxy resin, phenol resin, melamine resin, xylene resin, furan resin, cyanate ester resin and the like. In particular, epoxy resin and phenol resin are preferable because they have excellent insulating properties. The control of the softening point property requires the control of the compatibility, and an appropriate method is to appropriately select the structures and molecular weights of these thermosetting resins.

The epoxy resin is not particularly limited as long as it has two or more epoxy groups in one molecule, but bisphenol F, bisphenol A, bisphenol S,
Diglycidyl ethers such as resorcinol, dihydroxynaphthalene, dicyclopentadiene diphenol, dicyclopentadiene dixylenol, epoxidized phenol novolac, epoxidized cresol novolac, epoxidized trisphenylol methane, epoxidized tetraphenylol ethane, epoxidized metaxylene Alicyclic epoxies such as diamine and cyclohexane epoxide,
Etc. You may use these epoxy resins in mixture of 2 or more types. It is preferable to use those having a weight average molecular weight of 800 or less in order to impart transparency in the B stage. 800 or less and 800
Larger ones may be blended and used. The molecular weight referred to here is a value measured by GPC (gel permeation chromatography) and calculated in terms of polystyrene. In addition, structurally bisphenol A
Type and dicyclopentadiene type are preferred because they are relatively compatible with any resin and improve transparency. Further, in order to impart flame retardancy, it is effective to use a halogenated epoxy resin, particularly a brominated epoxy resin. At this time, although flame retardancy can be imparted only by the brominated epoxy resin, the heat resistance of the adhesive is greatly reduced, so that it is effective to use a mixed system with a non-brominated epoxy resin. Examples of brominated epoxy resins include tetrabromobisphenol A
And a brominated phenol novolac type epoxy resin such as "BREN" -S (manufactured by Nippon Kayaku Co., Ltd.). These brominated epoxy resins may be used as a mixture of two or more in consideration of the bromine content and the epoxy equivalent.

As the phenol resin, known phenol resins such as novolac type phenol resin and resol type phenol resin can be used. For example, alkyl-substituted phenols such as phenol, cresol, pt-butylphenol, nonylphenol and p-phenylphenol, cyclic alkyl-modified phenols such as terpenes and dicyclopentadiene, hetero groups such as nitro groups, halogen groups, cyano groups and amino groups. Those having a functional group containing atoms, those having a skeleton such as naphthalene, anthracene,
Examples of the resin include polyfunctional phenols such as bisphenol F, bisphenol A, bisphenol S, resorcinol, and pyrogallol.

The amount of the thermosetting resin added is 10
5 to 400 parts by weight, preferably 20 to 0 parts by weight
It is 200 parts by weight. When the amount of the thermosetting resin added is less than 5 parts by weight, the elastic modulus is significantly lowered at high temperature, and the semiconductor integrated circuit connecting substrate is deformed during the use of the device on which the semiconductor device is mounted, and it is handled in the processing step. Is not preferable because it lacks workability. If the addition amount of the thermosetting resin exceeds 400 parts by weight, the elastic modulus is high, the linear expansion coefficient is small, and the thermal stress relaxation effect is small, which is not preferable.

Addition of a curing agent and a curing accelerator for epoxy resin and phenol resin to the adhesive layer of the present invention is not limited at all. For example, 3,3 ', 5,5'-
Tetramethyl-4,4'-diaminodiphenylmethane,
3,3 ', 5,5'-tetraethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-5,5'-
Diethyl-4,4'-diaminodiphenylmethane, 3,
3'-dichloro-4,4'-diaminodiphenylmethane, 2,2 ', 3,3'-tetrachloro-4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminobenzophenone ,
3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminobenzophenone,
Aromatic polyamines such as 3,4,4'-triaminodiphenyl sulfone, boron trifluoride amine complexes such as boron trifluoride triethylamine complex, 2-alkyl-4-methylimidazole, 2-phenyl-4-alkylimidazole Known compounds such as imidazole derivatives such as phthalic anhydride, organic acids such as phthalic anhydride and trimellitic anhydride, dicyandiamide, and triphenylphosphine can be used. You may use these individually or in mixture of 2 or more types. The addition amount is preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of the adhesive composition.

In the present invention, by adding an inorganic filler to the adhesive layer, reflow resistance, processability such as punchability, thermal conductivity and flame retardancy can be further improved. The inorganic filler is not particularly limited as long as it does not impair the properties of the adhesive, and specific examples thereof include silica,
Aluminum oxide, silicon nitride, aluminum hydroxide,
Examples thereof include gold, silver, copper, iron, nickel, silicon carbide, aluminum nitride, titanium nitride and titanium carbide. Above all,
Silica, aluminum oxide, silicon nitride, silicon carbide and aluminum hydroxide are preferably used. Here, the silica may be amorphous or crystalline, and it is not limited to properly use it depending on the characteristics of each. These inorganic fillers may be surface-treated with a silane coupling agent or the like for the purpose of improving heat resistance and adhesiveness. Moreover, the shape of the inorganic filler is not particularly limited, and a crushed system, a spherical shape, a scaly shape, or the like is used, but a crushed system is preferably used. The term "crush" as used herein refers to a shape that is not spherical (not rounded). The particle size of the inorganic filler is not particularly limited, but an average particle size of 3 μm or less and a maximum particle size of 10 μm or less are preferably used in terms of reliability such as dispersibility and coating property, reflow resistance, and heat cycle property. Further, it is more effective to use together fillers having different average particle diameters from the viewpoint of fluidity and dispersibility. The particle size was measured with a Horiba LA500 laser diffraction type particle size distribution meter. The average particle size as used herein is defined as a particle size (median size) corresponding to 50% of the cumulative distribution expressed as a percentage (%) by measuring the particle size distribution based on the sphere equivalent volume. In the particle size distribution referred to here, the particle size is displayed on a volume basis in a 56-part logarithmic display (0.1 to 200 μm).
m). The maximum particle size is defined by the particle size corresponding to 100% of the cumulative distribution expressed as a percentage (%) in the particle size distribution defined by the average particle size. The measurement sample is assumed to be particles that have been clouded in ion-exchanged water and ultrasonically dispersed for 10 minutes.
In addition, the measurement was performed by adjusting the refractive index of 1.1 and the light transmittance to a reference value (about 70%, which has already been set in the apparatus). Further, the compounding amount is preferably 2 to 60 parts by weight, more preferably 5 to 50 parts by weight, based on the whole adhesive composition.

In the present invention, by adding a silane coupling agent to the adhesive layer, it is possible to improve the adhesive strength to various metals such as copper and rigid substrates such as glass epoxy substrates. The silane coupling agent is represented by the following formula (1).

[0029]

[Chemical 1]

Examples of the reactive group entering X include a vinyl group, an epoxy group, a styryl group, an acryloxy group amino group, a methacryl group, a mercapto group and an isocyanate group. Of these, amino groups and epoxy groups are preferable from the viewpoint of adhesiveness. As a reactive group entering OR, a methoxy group,
Examples thereof include an ethoxy group.

In addition to the above components, addition of organic and inorganic components such as antioxidants and ion scavengers is not limited to the extent that the characteristics of the adhesive are not impaired. Inorganic fine particles include metal hydroxides such as magnesium hydroxide and calcium aluminate hydrate, zirconium oxide, zinc oxide, antimony trioxide, antimony pentoxide, magnesium oxide, titanium oxide, iron oxide and cobalt oxide. Examples thereof include metal oxides such as chromium oxide and talc, inorganic salts such as calcium carbonate, metal fine particles such as aluminum, carbon black and glass. Organic components include styrene, NBR rubber, acrylic rubber, polyamide, polyimide and silicone. Cross-linked polymers such as Further, the use of an antioxidant is effective in the present invention. The antioxidant is not particularly limited as long as it imparts an antioxidant function, a phenolic antioxidant,
Known antioxidants such as thioether-based antioxidants, phosphorus-based antioxidants and amine-based antioxidants can be used. In the case of a resin containing a double bond such as NBR rubber,
When left at high temperature for a long time, crosslinking of the double bond portion gradually progresses and the adhesive film tends to become brittle, but these reactions can be suppressed by using an antioxidant. These organic and inorganic components may be used alone or in 2
You may use it in mixture of 2 or more types. Considering dispersion stability, the average particle size of the fine particle component is preferably 0.2 to 5 μm. Moreover, the compounding quantity is 0.1 to 50 of the whole adhesive composition.
Parts by weight are suitable.

The adhesive sheet for a semiconductor device of the present invention is
The adhesive composition for a semiconductor device of the present invention is used as an adhesive layer and has at least one peelable protective film layer. For example, a two-layer structure of protective film layer / adhesive layer or a three-layer structure of protective film layer / adhesive layer / protective film layer corresponds to this (FIG. 2). The adhesive layer includes not only a single film of the adhesive composition but also a composite structure in which an insulating film such as polyimide is laminated. The degree of cure of the adhesive sheet may be adjusted by heat treatment. The adjustment of the degree of curing has the effect of preventing excessive flow of the adhesive when adhering the adhesive sheet to the wiring board or the IC, and preventing foaming due to moisture during heat curing.

The term "protective film layer" as used herein means that before an adhesive layer is attached to a wiring board layer (TAB tape or the like) consisting of an insulator layer and a conductor pattern or a layer (stiffener etc.) where the conductor pattern is not formed. , Is not particularly limited as long as it can be peeled without impairing the form and function of the adhesive layer, for example, polyester, polyolefin, polyphenylene sulfide, polyvinyl chloride, polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, polyvinyl butyral, polyvinyl acetate. , Polyvinyl alcohol, polycarbonate, polyamide, polyimide, polymethylmethacrylate, and other plastic films, films obtained by coating these with a release agent such as silicone or a fluorine compound, and these films. Paper laminated with arm, paper and the like impregnated or coated with a releasing property of a certain resin. More preferably, the protective film layer is colored. Since it is possible to visually confirm whether the protective film has been peeled off, it is possible to prevent forgetting to peel it off.

When protective film layers are provided on both sides of the adhesive layer, F ₁ -F ₂ where F ₁ and F ₂ (F ₁ > F ₂ ) are the peeling forces of the protective film layers to the adhesive layer. Is preferably 5 Nm ^-1 or more, more preferably 15 Nm ^-1 or more. When F ₁ -F ₂ is less than 5 Nm ^-1 ,
It is not preferable because which side of the protective film layer the release surface is on is not stable and becomes a serious problem in use. Also,
The peeling forces F ₁ and F ₂ are preferably ^{1 to} 200 Nm ^-1
, And more preferably 3 to 100 Nm ⁻¹ . 1 Nm
If it is lower than ^{-1, the} protective film layer may come off, resulting in 200
If it exceeds Nm ^-1 , peeling is unstable and the adhesive layer may be damaged, which is not preferable.

Next, an example of an adhesive sheet for a semiconductor device and a method for manufacturing a semiconductor device using the adhesive composition of the present invention will be described.

(1) Adhesive sheet (a) A coating composition prepared by dissolving the adhesive composition of the present invention in a solvent,
It is coated on a polyester film having releasability and dried. It is preferable to apply the adhesive layer so that the thickness thereof is 10 to 100 μm. Drying conditions are 100-200
C, 1 to 5 minutes. The solvent is not particularly limited, but aromatic compounds such as toluene, xylene and chlorobenzene, ketone compounds such as methyl ethyl ketone and methyl isobutyl ketone,
An aprotic polar solvent such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc., or a mixture thereof is preferable.

(B) A polyester or polyolefin-based protective film layer having releasability having a weaker peeling strength is laminated on the film of (a) to obtain the adhesive sheet of the present invention. When the adhesive thickness is further increased, the adhesive sheets may be laminated multiple times. When creating a composite structure in which an insulating film such as polyimide is laminated in addition to a single film, the adhesive sheet is laminated on the insulating film as described above, or it is created by directly coating both surfaces of the insulating film. You may. After lamination, the degree of curing may be adjusted by, for example, performing heat treatment at 40 to 70 ° C. for about 20 to 200 hours.

(2) Semiconductor device (a) An adhesive copper tape for TAB is laminated with an electrolytic copper foil of 35 to 12 μm under conditions of 130 to 170 ° C. and 0.1 to 0.5 MPa, and then in an air oven. 80-1
Heated at 70 ℃, and then treated with copper foil TA
Create B tape. Photoresist film formation, etching, resist stripping, electrolytic nickel plating, electrolytic gold plating, and solder resist film formation are each performed on the copper foil surface of the obtained TAB tape with copper foil by a conventional method to prepare a wiring board.

(B) The adhesive sheet obtained in (1) is thermocompression bonded to the wiring board of (a), and the IC is thermocompression bonded to the opposite surface of the adhesive sheet. 120-18 in this state
Heat cure at 0 ° C.

(C) 110 to 200 IC and wiring board
After performing wire bonding connection under the condition of 100 ° C. and 150 kHz, resin sealing is performed.

(D) Finally, solder balls were mounted by reflow to obtain a semiconductor device of the present invention.

[0042]

The present invention will be described below with reference to examples.
The invention is not limited to these examples. The evaluation method will be described before the description of the examples.

Evaluation method (1) Preparation of pattern tape for evaluation: tape with adhesive for TAB (# 7100, (type 31N0-00FS),
Toray Co., Ltd.) and 18 μm electrolytic copper foil at 140 ° C.
Lamination was performed under the condition of 1 MPa. Then, in an air oven, 80 ° C, 3 hours, 100 ° C, 5 hours, 150 ° C, 5
A heating and curing treatment was sequentially performed for a time to prepare a TAB tape with a copper foil. Photoresist film formation, etching, resist stripping, electrolytic nickel plating, and electrolytic gold plating were each performed on the copper foil surface of the obtained TAB tape with copper foil by a conventional method to prepare a pattern tape sample for evaluation. Nickel plating thickness is 3μm, gold plating thickness is 1μ
m.

(2) Reflow resistance: After laminating the adhesive sheet of the present invention on the back surface of the evaluation pattern tape of (1) under the conditions of 130 ° C. and 0.1 MPa, an IC having an aluminum electrode pad was used. A semiconductor device for evaluation having the structure shown in FIG. 1 was prepared. A 30 mm square sample prepared by this method was conditioned for 48 hours in an atmosphere of 85 ° C. and 85% RH, and then quickly passed through an infrared reflow oven with a maximum temperature of 265 ° C. for 10 seconds to confirm swelling and peeling. did.

(3) Thermal cycle property: 30 semiconductor devices samples having a size of 30 mm square prepared by the method of (2) above were prepared for each level, and a thermal cycle tester (PL-3 manufactured by Tabai Espec Co., Ltd.) was prepared. Mold), at -65 ° C to 150
The treatment was carried out under conditions of 30 ° C., minimum temperature and maximum temperature for 30 minutes each, and the occurrence of peeling was evaluated. 100 cycles, 300
Samples were taken out at the end of each of the cycles, 500 cycles, and 800 cycles, and the occurrence of peeling was evaluated. Three
If even one of the 0 pieces has been peeled off, N. G. And

(4) Haze (haze value): An adhesive single film having a thickness of 50 μm was prepared, and haze was measured by a method according to JIS K7105. The measuring equipment is Suga Test Machine Co., Ltd.
A direct reading haze computer (model: HGM-2DP) was used. The change ratio is (A) after heating and curing the sheet adhesive composition at 170 ° C. for 2 hours and (B).
Was calculated as the ratio (A / B). The curing conditions of the sample were 170 ° C. and 2 hours as described above.

(5) Evaluation of curing status (productivity): 20 mm prepared by the method of (2) above, using a dummy chip like an IC instead of an IC having an aluminum electrode pad
In each of the corner evaluation semiconductor device samples, five sheets of cured sheet adhesive and five sheets of uncured adhesive are prepared. Mark the sample to see if it is cured. Only the adhesive portion of the sample was taken out, and if it was possible to recognize 100% whether it was cured or not, it was marked with ◯, and if not, it was marked with x.

Examples 1 to 9 and Comparative Examples 1 and 2 (Preparation of Adhesive Sheet) Each inorganic filler as shown in Table 1 was mixed with toluene and then sand milled to prepare a dispersion. Methyl ethyl ketone in an amount equal to that of each thermoplastic resin, thermosetting resin, curing agent, curing accelerator, other additive and dispersion liquid was added to this dispersion liquid at a composition ratio shown in Table 1, and stirred at 30 ° C. , And mixed to prepare an adhesive solution. This adhesive solution was applied with a bar coater to a 38 µm thick polyethylene terephthalate film with a silicone release agent ("Film Vina" G manufactured by Fujimori Industry Co., Ltd.).
T) to a dry thickness of about 50 μm,
It was dried at 0 ° C. for 4 minutes, and a protective film was attached to it to prepare an adhesive sheet for a semiconductor device of the present invention. Table 1 shows each composition and characteristics.

(Production of Semiconductor Device) Tape with adhesive for TAB (type # 7100, (31N0-00FS),
Toray Co., Ltd.) and 18 μm electrolytic copper foil at 140 ° C.
Lamination was performed under the condition of 1 MPa. Then, in an air oven, 80 ° C, 3 hours, 100 ° C, 5 hours, 150 ° C, 5
A heating and curing treatment was sequentially performed for a time to prepare a TAB tape with a copper foil. Photoresist film formation, etching, resist stripping, electrolytic nickel plating, electrolytic gold plating, and photosolder resist processing were each performed on the copper foil surface of the obtained TAB tape with copper foil by a conventional method to prepare a pattern tape. Nickel plating thickness is 3μm,
The gold plating thickness was 1 μm. Subsequently, after laminating the adhesive sheet having each adhesive described in Table 1 on the back surface of the pattern tape under the conditions of 130 ° C. and 0.1 MPa, the IC having an aluminum electrode pad was 170 ° C. and 0.3 MPa.
It thermocompression-bonded to the adhesive agent sheet on condition of MPa. Next, heat curing treatment was performed at 170 ° C. for 2 hours in an air oven. Subsequently, a 25 μm gold wire was added to this at 150 ° C.
Bonding was performed at 110 kHz. Further, it was sealed with a liquid sealing resin (“Chip coat” 8118, manufactured by NAMICS CORPORATION). Finally, a solder ball was mounted to fabricate a semiconductor device having the structure shown in FIG.

Details of each material used in Examples and Comparative Examples are shown below. A. Thermoplastic resin 1. SG-280DR (manufactured by Teikoku Chemical Industry Co., Ltd.): Acrylic rubber containing butyl acrylate as a main component and containing a carboxyl group 2. SGP-3 (manufactured by Teikoku Chemical Industry Co., Ltd.): Epoxy group-containing acrylic rubber containing butyl acrylate as a main component 3. XF-1834 (manufactured by Tope Co., Ltd.): Hydroxyl group-containing acrylic rubber containing ethyl acrylate as a main component 4. PNR-1H (manufactured by JSR Corporation): NBR containing a carboxyl group 5. A1095 (manufactured by Nippon Mektron Co., Ltd.): Acrylic rubber containing ethyl acrylate as a main component and containing active chlorine groups.

B. Thermosetting resin 1. Epoxy resin A: Bisphenol A type epoxy resin ("Epicoat" 82 manufactured by Japan Epoxy Resins Co., Ltd.)
8, epoxy equivalent: 140) 2. Epoxy resin B: Bisphenol A type epoxy resin ("Epicoat" 10 manufactured by Japan Epoxy Resins Co., Ltd.)
01, epoxy equivalent: 478) 3. Epoxy resin C: dicyclopentadiene type epoxy resin (Nippon Kayaku Co., Ltd. XD-1000-2L, epoxy equivalent: 240) 4. Phenol resin: Phenol novolac resin (KH6021 manufactured by Dainippon Ink and Chemicals, Inc.).

C. Inorganic filler 1. Aluminum hydroxide (Al (OH) ₃ ): (average particle size: 1 μm, maximum particle size: 6 μm) 1. Silica A (Fuji Silysia Chemical Ltd .: "SYLY
SIA "310P): (Average particle size: 2.7 μm, maximum particle size: 10 μm, crushed silica) 3. Silica B (manufactured by Admatechs Co., Ltd .: SO-E)
1): (average particle size: 0.3 μm, maximum particle size: 1 μm, spherical silica) 4. Silica C (manufactured by Admatechs Corporation: SO-E
2): (average particle size: 0.5 μm, maximum particle size: 2 μm, spherical silica) Silica D (manufactured by Admatechs Corporation: SO-C
5): (average particle size: 1.5 μm, maximum particle size: 8 μm, spherical silica).

D. Hardener, hardening accelerator 1.4,4'-DDS: 4,4'-diaminodiphenyl sulfone 2. C11z: 2-undecylimidazole 3. TPP: triphenylphosphine 4. DDM: Diaminodiphenylmethane 5.2E4MZ: 2-Ethyl-4-methylimidazole E.I. Silane coupling agent A: Shin-Etsu Chemical Co., Ltd .: KBE-603 (N-β
(Aminoethyl) γ-aminopropyltrimethoxysilane) B: Shin-Etsu Chemical Co., Ltd .: KBE-402 (γ-glycidoxypropylmethyldiethoxysilane) C: Shin-Etsu Chemical Co., Ltd .: KBM-503 (Γ-methacryloxypropyltriethoxysilane)

[0054]

[Table 1]

The adhesive compositions for semiconductor devices obtained from the examples and comparative examples of Table 1 according to the present invention are excellent in transparency visibility before and after curing, adhesive strength, reflow resistance, thermal cycleability and workability. I know that

[0056]

The adhesive composition of the present invention, whose transparency changes before and after curing, is excellent in reflow resistance, thermal cycleability and work efficiency. Furthermore, the production efficiency of semiconductor devices can be improved by the adhesive composition for semiconductor devices of the present invention.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of one embodiment of a BGA type semiconductor device using the adhesive composition for a semiconductor device and the adhesive sheet for a semiconductor device of the present invention.

FIG. 2 is a cross-sectional view of one embodiment of the adhesive sheet for a semiconductor device of the present invention.

[Explanation of symbols]

1 Semiconductor integrated circuit 2,9 Adhesive layer composed of the adhesive composition of the present invention 3 wiring board layers 4 Conductor for solder ball connection 5 Bonding wire 6 solder balls 7 Sealing resin 8 Protective film layer constituting the adhesive sheet of the present invention

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J004 AA10 AA12 AA13 DB02 FA05                 4J040 DF001 EB032 EC002 GA05                       GA07 GA11 GA14 GA29 HA026                       HA136 HA206 HA306 HD32                       JA09 NA20

Claims (10)

[Claims] 1. A sheet adhesive composition having a temperature of 170 ° C.
An adhesive composition for a semiconductor device, wherein the haze change ratio (A / B) between the haze (A) after being heat-cured for 2 hours and the B-stage haze (B) is 1.2 or more. 2. The adhesive composition for a semiconductor device according to claim 1, wherein the haze value of the B stage haze (B) in the sheet adhesive composition is 80 or less. 3. An adhesive composition comprising an acrylic acid and / or methacrylic acid ester having a side chain of 1 to 8 carbon atoms and an epoxy group, a hydroxyl group, a carboxyl group, an amino group, a methylol group, a vinyl group, a silanol group, The adhesive composition for a semiconductor device according to claim 1, comprising a resin containing at least one functional group selected from an isocyanate group as an essential component. 4. The adhesive composition for a semiconductor device according to claim 1, which contains a silane coupling agent. 5. The adhesive composition for a semiconductor device according to claim 1, which contains at least one kind of inorganic filler selected from silica, aluminum oxide, aluminum hydroxide, silicon nitride and silicon carbide. . 6. The adhesive composition for a semiconductor device according to claim 5, wherein the inorganic filler has an average particle diameter of 3 μm or less. 7. The adhesive composition for a semiconductor device according to claim 5, wherein the inorganic filler is crushed silica. 8. An adhesive sheet for a semiconductor device, which comprises the adhesive composition for a semiconductor device according to claim 1 as an adhesive layer and has at least one peelable protective film layer. 9. A substrate for semiconductor connection, which uses the adhesive composition for a semiconductor device according to claim 1. 10. A semiconductor device using the substrate for semiconductor connection according to claim 9.